Solubility and activity of oxygen in liquid nickel in equilibrium with -Al2O3 and NiO.(1+x)Al2O3

The limiting solubility of oxygen in liquid nickel in equilibrium withα-alumina and nickel aluminate has been measured by inert gas fusion analysis of suction samples in the temperature range 1730 to 1975 K. The corresponding oxygen potential has been monitored by a solid electrolyte cell consisting of calcia stabilized zirconia as the electrolyte and Mo + MoO2 as the reference electrode. The results can be summarized by the following equations: log(at. pct O) = \frac - 10,005T + 4.944 ( ±0.015)log(atpctO)=T−10005+4944(0015) % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn DmO2 /4.606RT = log P O2 1/2 = \frac - 13,550T + 4.411 ( ±0.009)O24606RT=logPO212=T−13550+4411(0009) From simultaneous measurements of the potential and concentration of oxygen in melts, not in thermodynamic equilibrium with alumina and aluminate phases, information on the composition dependence of the activity coefficient and the standard free energy of solution of oxygen is obtained. For the reaction, $\frac{1}{2} O_2 \to \underset{\raise0.3em\hbox{$Missing close brace ΔG o = -72,930 - 7.11T (±840) J gr.at.–1 = + 0.216 at. pct OlogfO=T−500+0216atpctO where the standard state for dissolved oxygen is that which makes the value of activity equal to the concentration (in at. pct) in the limit as concentration approaches zero. The oxygen solubility in liquid nickel in equilibrium with solid NiO, evaluated from thermodynamic data, is compared with information reported in the literature. Implications of the results to the deoxidation equilibria of aluminum in nickel are discussed.

Measurement of Gibbs energies of formation of CoF2 and MnF2 using a new composite dispersed solid electrolyte

Gibbs energies of formation of CoF2 and MnF2 have been measured in the temperature range from 700 to 1100 K using Al2O3-dispersed CaF2 solid electrolyte and Ni+NiF2 as the reference electrode. The dispersed solid electrolyte has higher conductivity than pure CaF2 thus permitting accurate measurements at lower temperatures. However, to prevent reaction between Al2O3 in the solid electrolyte and NiF2 (or CoF2) at the electrode, the dispersed solid electrolyte was coated with pure CaF2, thus creating a composite structure. The free energies of formation of CoF2 and MnF2 are (± 1700) J mol−1; {fx37-1} The third law analysis gives the enthalpy of formation of solid CoF2 as ΔH° (298·15 K) = −672·69 (± 0·1) kJ mol−1, which compares with a value of −671·5 (± 4) kJ mol−1 given in Janaf tables. For solid MnF2, ΔH°(298·15 K) = − 854·97 (± 0·13) kJ mol−1, which is significantly different from a value of −803·3 kJ mol−1 given in the compilation by Barinet al.

Measurement of the Gibbs energy of formation of URh3 using an oxide solid electrolyte

The Gibbs' energy offormation of the intermetallic compound URh3has been measured in the temperature range 980 to 1320 K using an oxide solid state cell incorporating yttria-doped thoria as the solid electrolyte and a mixture of manganese and manganese oxide as the reference electrode. The cell can be represented as Pt, Mn + MnO I (Y203)Th02 I Rh + URh3 + U02 + x' Rh, Pt The reversible emf of the cell was a linear function of temperature E = 15.60 +0.0237 T (±0.8) mY. Using auxiliary thermodynamic data for MnO and U02+ x the Gibbs' energy of formation of URh3 from component metals has been computed. The results can be expressed by the equation L'.G?< URh3 > = -316240 + 13.22 T (± 3000) J mol-1. The "third-law" enthalpy of formation of URh3at 298 K is -293.2 (± 4) kJ mol-1, significantly more negative than the value of -181.5 kJ mol-1 calculated using Miedema's model.

Low oxygen potential boundary for the stability of YBA2Cu3O7−δ

On lowering the oxygen potential, the tetragonal phase of YBa2Cu3O7−δ was found to decompose into a mixture of Y2BaCuO5, BaCuO2 and BaCu2O2 in the temperature range 773–1173 K. The 123 compound was contained in a closed crucible of yttria-stabilized zirconia in the temperature range 773–1073 K. Oxygen was removed in small increments by coulometric titration through the solid electrolyte crucible at constant temperature. The oxygen potential was calculated from the open circuit e.m.f. of the solid state cell after successive titrations. Pure oxygen at a pressure of 1.01 × 105 Pa was used as the reference electrode. The decomposition of the 123 compound manifested as a plateau in oxygen potential. The decomposition products were identified by X-ray diffraction. At temperatures above 1073 K there was some evidence of reaction between the 123 compound, solid electrolyte crucible and platinum. For measurements above 1073 K, the 123 compound was contained in a magnesia crucible placed in a closed outer silica tube. The oxygen potential in the gas phase above the 123 compound was controlled and measured by a solid state cell based on yttria-stabilized zirconia which served both as a pump and sensor. The lower oxygen potential limit for the stability of the 123 compound is given by View the MathML source The oxygen non-stoichiometric parameter δ for the 123 compound has a value of 0.98 (View the MathML source) at dissociation.

Refinement of thermodynamic properties of ReO2

The standard Gibbs energy of formation of ReO2 in the temperature range from 900 to 1200 K has been determined with high precision using a novel apparatus incorporating a buffer electrode between reference and working electrodes. The role of the buffer electrode was to absorb the electrochemical flux of oxygen through the solid electrolyte from the electrode with higher oxygen chemical potential to the electrode with lower oxygen potential. It prevented the polarization of the measuring electrode and ensured accurate data. The Re+ReO2 working electrode was placed in a closed stabilized-zirconia crucible to prevent continuous vaporization of Re2O7 at high temperatures. The standard Gibbs energy of the formation of ReO2 can be represented by the equation View the MathML source Accurate values of low and high temperature heat capacity of ReO2 are available in the literature. The thermal data are coupled with the standard Gibbs energy of formation, obtained in this study, to evaluate the standard enthalpy of formation of ReO2 at 298.15 K by the ‘third law’ method. The value of standard enthalpy of formation at 298.15 K is: View the MathML source(ReO2)/kJ mol−1=−445.1 (±0.2). The uncertainty estimate includes both random (2σ) and systematic errors.

Thermodynamic properties of calcium titanates: CaTiO3, Ca4Ti3O10, and Ca3Ti2O7

The chemical potentials of CaO in two-phase fields (TiO2 + CaTiO3), (CaTiO3 + Ca4Ti3O10), and (Ca4Ti3O10 + Ca3Ti2O7) of the pseudo-binary system (CaO + TiO2) have been measured in the temperature range (900 to 1250) K, relative to pure CaO as the reference state, using solid-state galvanic cells incorporating single crystal CaF2 as the solid electrolyte. The cells were operated under pure oxygen at ambient pressure. The standard Gibbs free energies of formation of calcium titanates, CaTiO3, Ca4Ti3O10, and Ca3Ti2O7, from their component binary oxides were derived from the reversible e.m.f.s. The results can be summarised by the following equations: CaO(solid) + TiO2(solid) → CaTiO3(solid), ΔG° ± 85/(J · mol−1) = −80,140 − 6.302(T/K); 4CaO(solid) + 3TiO2(solid) → Ca4Ti3O10(solid), ΔG° ± 275/(J · mol−1) = −243,473 − 25.758(T/K); 3CaO(solid) + 2TiO2(solid) → Ca3Ti2O7(solid), ΔG° ± 185/(J · mol−1) = −164,217 − 16.838(T/K). The reference state for solid TiO2 is the rutile form. The results of this study are in good agreement with thermodynamic data for CaTiO3 reported in the literature. For Ca4Ti3O10 Gibbs free energy of formation obtained in this study differs significantly from that reported by Taylor and Schmalzried at T = 873 K. For Ca3Ti2O7 experimental measurements are not available in the literature for direct comparison with the results obtained in this study. Nevertheless, the standard entropy for Ca3Ti2O7 at T = 298.15 K estimated from the results of this study using the Neumann–Koop rule is in fair agreement with the value obtained from low-temperature heat capacity measurements.

Surface chemical and adsorption studies using Thiobacillus ferrooxidans with reference to bacterial adhesion to sulfide minerals

Adhesion of Thiobacillus ferrooxidans to pyrite and chalcopyrite in relation to its importance in bioleaching and bioflotation has been studied. Electrokinetic studies as well as FT-IR spectra suggest that the surface chemistry of Thiobacillus ferrooxidans depends on bacterial growth conditions. Sulfur-,Pyrite- and chalcopyrite-grown Thiobacillus ferrooxidans were found to be relatively more hydrophobic. The altered surface chemistry of Thiobacillus ferrooxidans was due to secretion of newer and specific proteinaceous compounds. The adsorption density corresponds to a monolayer coverage in a horizontal orientation of the cells. The xanthate flotation of pyrite in presence of Thiobacillus ferrooxidans is strongly depressed where as the cells have insignificant effect on chalcopyrite flotation. This study demonstrate that: (a)Thiobacillus ferrooxidans cells can be used for selective flotation of chalcopyrite from pyrite and importantly at natural pH values. (b)Sulfur-grown cells exhibits higher leaching kinetics than ferrous ion-grown cells.

Low cost calibrated mechanical noisemaker for hearing screening of neonates in resource constrained settings

Background & objectives: There is a need to develop an affordable and reliable tool for hearing screening of neonates in resource constrained, medically underserved areas of developing nations. This study valuates a strategy of health worker based screening of neonates using a low cost mechanical calibrated noisemaker followed up with parental monitoring of age appropriate auditory milestones for detecting severe-profound hearing impairment in infants by 6 months of age. Methods: A trained health worker under the supervision of a qualified audiologist screened 425 neonates of whom 20 had confirmed severe-profound hearing impairment. Mechanical calibrated noisemakers of 50, 60, 70 and 80 dB (A) were used to elicit the behavioural responses. The parents of screened neonates were instructed to monitor the normal language and auditory milestones till 6 months of age. This strategy was validated against the reference standard consisting of a battery of tests - namely, auditory brain stem response (ABR), otoacoustic emissions (OAE) and behavioural assessment at 2 years of age. Bayesian prevalence weighted measures of screening were calculated. Results: The sensitivity and specificity was high with least false positive referrals for. 70 and 80 dB (A) noisemakers. All the noisemakers had 100 per cent negative predictive value. 70 and 80 dB (A) noisemakers had high positive likelihood ratios of 19 and 34, respectively. The probability differences for pre- and post- test positive was 43 and 58 for 70 and 80 dB (A) noisemakers, respectively. Interpretation & conclusions: In a controlled setting, health workers with primary education can be trained to use a mechanical calibrated noisemaker made of locally available material to reliably screen for severe-profound hearing loss in neonates. The monitoring of auditory responses could be done by informed parents. Multi-centre field trials of this strategy need to be carried out to examine the feasibility of community health care workers using it in resource constrained settings of developing nations to implement an effective national neonatal hearing screening programme.

Recent Developments in the Chemistry and Biology of G-Quadruplexes with Reference to the DNA Groove Binders

DNA is the chemotherapeutic target for treating diseases of genetic origin. Besides well-known double-helical structures (A, B, Z, parallel stranded-DNA etc.), DNA is capable of forming several multi-stranded structures (triplex, tetraplex, i-motif etc.) which have unique biological significance. The G-rich 3'-ends of chromosomes, called telomeres, are synthesized by telomerase, a ribonucleoprotein, and over-expression of telomerase is associated with cancer. The activity of telomerase is suppressed if the G-rich region is folded into the four stranded structures, called G-quadruplexes (G4-DNAs) using small synthetic ligands. Thus design and synthesis of new G4-DNA ligands is an attractive strategy to combat cancer. G4-DNA forming sequences are also prevalent in other genomic regions of biological significance including promoter regions of several oncogenes. Effective gene regulation may be achieved by inducing a G4-DNA structure within the G-rich promoter sequences. To date, several G4-DNA stabilizing ligands are known. DNA groove binders interact with the duplex B-DNA through the grooves (major and minor groove) in a sequence-specific manner. Some of the groove binders are known to stabilize the G4-DNA. However, this is a relatively under explored field of research. In this review, we focus on the recent advances in the understanding of the G4-DNA structures, particularly made from the human telomeric DNA stretches. We summarize the results of various investigations of the interaction of various organic ligands with the G4-DNA while highlighting the importance of groove binder-G4-DNA interactions.

An experimental study on cracking evolution in concrete and cement mortar by the b-value analysis of acoustic emission technique

Notched three point bend (TPB) specimens made with plain concrete and cement mortar were tested under crack mouth opening displacement (CMOD) control at a rate of 0.0004 mm/s and simultaneously acoustic emissions (AE) released were recorded during the experiments. Amplitude distribution analysis of AE released during concrete was carried out to study the development of fracture process in concrete and mortar specimens. The slope of the log-linear frequency-amplitude distribution of AE is known as the AE based b-value. The AE based b-value was computed in terms of physical process of time varying applied load using cumulative frequency distribution (Gutenberg-Richter relationship) and discrete frequency distribution (Aki's method) of AE released during concrete fracture. AE characteristics of plain concrete and cement mortar were studied and discussed and it was observed that the AE based b-value analysis serves as a tool to identify the damage in concrete structural members. (C) 2012 Elsevier Ltd. All rights reserved.